Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/24—[b,e]-condensed with two six-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
  • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
  • C07D339/08—Six-membered rings

Definitions

• This invention relates to derivatives of propenoic acid useful in agriculture (especially as fungicides but also as plant growth regulators), to processes for preparing them, to fungicidal compounds containing them, and to methods of using them to combat fungi, especially fungal infections in plants, and to regulate plant growth.
• the invention provides a compound having the general formula (I): and stereoisomers thereof, wherein X and Y, which may be the same or different, are oxygen or sulphur; and A and B, which may be the same or different, are hydrogen, halogen, alkyl, alkoxy, optionally substituted phenyl, optionally substituted phenoxy, or optionally substituted benzyloxy.
• substituents which may be present on the phenyl rings include one or more of the following: halogen, C 1-4 alkyl, C 1-4 alkoxy, halo(C 1-4 )alkyl, cyano and nitro.
• substituents are chlorine and fluorine.
• a and B are both hydrogen and X and Y are the same; either both oxygen or both sulphur.
• the invention also includes compounds in which not both of A and B are hydrogen and also compounds in which one of X and Y is oxygen and the other is sulphur.
• the compounds of the invention contain a carbon-­carbon double bond, and are sometimes obtained in the form of mixtures of geometric isomers. However, these mixtures can be separated into individual isomers, and this invention embraces such isomers.
• the compounds of the invention can be prepared from compounds of general formula (IV) by the steps shown in Scheme I.
• Scheme I the terms X and Y are as defined above except where otherwise specified, and A and B are as defined above.
• compounds of formula (I) can be prepared by treatment of methyl ketoesters of general formula (II) with the phosphorane of formula (C6H5)3P:CH.OCH3 in a suitable solvent such as an ether (see, for example, EP-A-0044448).
• Methyl ketoesters of general formula (II) can be prepared by treatment of a lithiated species (III) with dimethyl oxalate in a suitable solvent such as an ether (for example, diethyl ether or tetrahydrofuran).
• a tetrahydrofuran solution of the lithiated species is added to a tetrahydrofuran solution of dimethyl oxalate, cooled to a temperature below 0°C, for example -10°C (see, for example, L M Weinstock, R B Currie and A V Lovell, Synth.Commun. 1981, 11 , 943).
• the lithiated species (III) can be prepared by direct lithiation of compounds (IV) using a strong lithium base such as n -butyl-lithium. Lithiation of phenoxyathiin occurs ortho to the C-O bond rather than the C-S bond to give the lithiated species (III) wherein X is sulphur and Y is oxygen. By contrast, lithiation of the 10-oxide or 10,10-dioxide derivatives of phenoxyathiin occurs ortho to the C-S bond to give a species (III) wherein X is oxygen and Y is SO or SO2 respectively (see, for example, "Comprehensive Heterocyclic Chemistry", Editors A R Katritzky and C W Rees, Vol.
• the compounds of the invention can also be prepared by the steps shown in scheme II. Throughout Scheme II the terms X, Y, A and B are as defined above.
• compounds of formula (I) may be prepared from acetates of general formula (VII) by treatment with methyl formate and a base followed by O -methylation, or from acetals of general formula (VIIa) by the elimination of the elements of methyl alcohol under acidic or basic conditions. [Both of these methods are described in detail in EP-A-0178826, as is the general procedure for preparing the acetals of formula (VIIa)].
• Acetates of general formula (VII) may be prepared from compounds of general formula (VI) by treatment with acidic methanol.
• Compounds of general formula (VI) may in turn be prepared from compounds of general formula (V) by reaction with methyl methylsulphinylmethyl sulphide and a base.
• the aldehydes of general formula (V) may be prepared by reaction of the lithium species of general formula (III) already described in Scheme I, with a formyl transfer reagent such as N , N -dimethylformamide or N -­formylmorpholine, in a suitable solvent such as THF, at a temperature of -70° to +20°C but preferably at -20° to 0°C.
• a formyl transfer reagent such as N , N -dimethylformamide or N -­formylmorpholine
• compounds of formulae (VIII) and (X) can be converted into compounds (IX) and (XI) respectively by treatment with elemental sulphur and a Lewis acid such as aluminium chloride (compare, for example, C M Suter and C E Maxwell, Organic Syntheses, Coll. Vol. 2 , 485).
• a Lewis acid such as aluminium chloride
• the formation of regioisomeric products is possible in the conversion of (X) into (XI) and, when the substituents A and B are unsymmetrically positioned, also in the conversion of (VIII) into (IX).
• the compounds of the invention of formula (I) may be made from appropriate precursors of formula (XII) in which the 3 fused rings are already present (Scheme IV).
• the invention includes the process hereinbefore described for preparing the compounds of the invention and the intermediate compounds having the formulae (II), (III), (V), (VII) and (VIIa) used therein.
• the compounds are active fungicides, and may be used to control one or more of the diseases: Pyricularia oryzae on rice.
• Puccinia recondita Puccinia striiformis and other rusts on wheat, Puccinia hordei , Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables and ornamental plants.
• cucumber cucumber
• Botrytis cinerea grey mould
• Alternaria species on vegetables e.g. cucumber
• oil seed rape apples
• tomatoes and other hosts Venturia inaequalis (scab) on apples.
• Some of the compounds have also shown a broad range of activities against fungi in vitro . They may have activity against various post-harvest diseases of fruit (e.g. Penicillium digitatum and italicum and Trichoderma viride on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes).
• post-harvest diseases of fruit e.g. Penicillium digitatum and italicum and Trichoderma viride on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes.
• the invention provides a method of combating fungi, which comprises applying to a plant, to a seed of a plant, or to the locus of the plant or seed, a fungicidally effective amount of a compounds of formula (I) as hereinbefore defined, or a composition containing the same.
• the compounds may also be useful as industrial (as opposed to agricultural) fungicides, e.g. in the prevention of fungal attack on wood, hides, leather and paint films.
• Some compounds exhibit plant growth regulating activity and may be deployed for this purpose, at appropriate rates of application.
• the invention provides a method of regulating plant growth which comprises applying to a plant, to a seed of a plant or to the locus of the plant or seed an effective amount of a plant growth regulating compound of formula (I).
• the compounds may be used directly for agricultural purposes but are more conveniently formulated into compositions using a carrier or diluent.
• the invention thus provides a fungicidal or plant growth regulator composition comprising a compound of general formula (I) as hereinbefore defined, and an acceptable carrier or diluent therefor.
• the compounds can be applied in a number of ways. For example they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules. Application can be to any part of the plant including the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted; or to the soil generally, to paddy water or to hydroponic culture systems.
• the invention compounds may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods.
• plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
• the compounds are preferably used for agricultural and horticultural purposes in the form of a composition.
• the type of composition used in any instance will depend upon the particular purpose envisaged.
• compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, diatomaceous earth and China clay.
• a solid diluent or carrier for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, diatomaceous earth and China clay.
• Such granules can be preformed granules suitable for application to the soil without further treatment.
• These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler.
• compositions for dressing seed may include an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methylpyrrolidone, propylene glycol or dimethylformamide).
• the compositions may also be in the form of wettable powders or water dispersible granules comprising wetting or dispersing agents to facilitate the dispersion in liquids.
• the powders and granules may also contain fillers and suspending agents.
• Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the mixture to water which may also contain a wetting or emulsifying agent.
• organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as isophorone, cyclohexanone, and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichlorethane, and alcohols such as furfuryl alcohol, butanol and glycol ethers.
• Suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent and including a suspending agent to stop the solid settling.
• compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, eg. fluorotrichloromethane or dichlorodifluoromethane.
• a propellant eg. fluorotrichloromethane or dichlorodifluoromethane.
• the invention compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.
• the compounds may be used in a micro­encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.
• the different compositions can be better adapted for various utilities.
• the invention compounds can be used as mixtures with fertilisers (eg. nitrogen-, potassium- or phosphorus-­containing fertilisers).
• Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound are preferred. Such granules suitably contain up to 25% by weight of the compound.
• the invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of general formula (I) or a salt or metal complex thereof.
• Wettable powders, emulsifiable concentrates and suspension concentrates will normally contain surfactants eg. a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.
• Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.
• Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates).
• Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol.
• Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
• Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carb-oxymethylcellulose), and swelling clays such as bentonite or attapulgite.
• compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use.
• These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
• the concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient may be used.
• compositions of this invention may contain other compounds having biological activity, eg. compounds having similar or complementary fungicidal activity or which plant possess plant growth regulating, herbicidal or insecticidal activity.
• a fungicidal compound which may be present in the composition of the invention may be one which is capable of combating ear diseases of cereals (eg. wheat) such as Septoria , Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple etc.
• cereals eg. wheat
• the composition can have a broader spectrum of activity than the compound of general formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I).
• fungicidal compounds which may be included in the composition of the invention are carbendazim, benomyl, thiophanate-methyl, thiabendazole, fuberidazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminium, fenarimol, iprodione, prothiocarb, procymidone, vinclozolin, penconazole, myclobutanil, propamocarb, R0151297, pyrazophos, ethirimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, triacetate salt of 1,1′-iminodi-(octamethylene)­diguanidine, buthiobate, propiconazole,
• the compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
• Suitable insecticides which may be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion, propaphos, monocrotophas, buprofezin, ethroproxyfen and cycloprothrin.
• Plant growth regulating compounds are compounds which control weeds or seedhead formation, or selectively control the growth of less desirable plants (eg. grasses).
• suitable plant growth regulating compounds for use with the invention compounds are the gibberellins (eg. GA3, GA4 or GA7), the auxins (eg. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (eg. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (eg. 2,4-D or MCPA), substituted benzoic acid (eg. triiodobenzoic acid), morphactins (eg.
• gibberellins eg. GA3, GA4 or GA7
• the auxins eg. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid
• the cytokinins eg. kinetin, diphenylurea, benzimidazole
• chlorfluoroecol maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids, dikegulac, paclobutrazol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg.
• chloromequat chlorphonium or mepiquatchloride ethephon, carbetamide, methyl-3,6- dichloroanisate, daminozide, asulam, abscisic acid, isopyrimol, 1-(4-­chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-­carboxylic acid, hydroxybenzonitriles (eg. bromoxynil), difenzoquat, benzoylprop-ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide, triapenthenol and tecnazene.
• hydroxybenzonitriles eg. bromoxynil
• difenzoquat benzoylprop-ethyl 3,6-dichloropicolinic acid
• fenpentezol inabenfide
• infrared and n.m.r. data are selective; no attempt is made to list every absorption.
• DMF N , N -dimethylformamide
• n -Butyl-lithium (12.6ml of 2.5M solution in hexane) was added over 15 minutes to a stirred solution of dibenzo- p -dioxin (5.0g; prepared from 2-chlorophenyl by the method of H Gilman and J J Dietrich, J.Am.Chem.Soc. , 1957, 79 , 1439) in a mixture of ether (15ml) and THF (30ml) at a temperature between 0 and 5°C. The resulting yellow solution was allowed to warm to room temperature and stirred for 5 hours, whereupon it darkened to a green-­brown colour.
• n-Butyl-lithium (11.25 ml of 1.6 M solution in hexane) was added dropwise over 5 minutes to a stirred solution of dibenzo- p -oxathiin (3.0g; prepared from diphenyl ether by the method of C M Suter and C E Maxwell, Organic Syntheses , Coll. Vol. 2 , 485) in THF (30 ml) at a temperature of between -10° and 0°C. After completion of the addition the reaction mixture was allowed to warm to room temperature and stirred for 4 hours. The solution was then cooled to -10°C and a solution of N -formylmorpholine (2.07g) in THF (20 ml) was added.
• reaction mixture was allowed to warm to room temperature, stirred for 1.5 hours, allowed to stand overnight, and then poured into water (200 ml). The mixture was extracted with ethyl acetate and the ethyl acetate extracts were washed with water, dried, and evaporated to give an orange semi-­solid. This solid was triturated with ether, and the insoluble material was filtered off.
• this oil (1.47g) was dissolved in DMF (10 ml), and potassium carbonate (1.25g) and dimethyl sulphate (0.57g) were added successively. The mixture was stirred at room temperature for 30 minutes, allowed to stand for 3 days, poured into water containing a little dilute hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate extract was washed with water, dried, and evaporated to give a yellow oil (1.55g). The oil was purified by high performance liquid chromatography on silica gel, eluting with 1:1 ethyl acetate : hexane, to give the title compound as a pale yellow solid (0.979g), mp.
• thianthrene 40.0g was formylated by successive treatment with n -butyl-lithium (127 ml of 1.6 M solution in hexane) and N -formylmorpholine to give, after work-up but without any form of purification, a yellow oil comprising 1-formyl­thianthrene and unreacted thianthrene (91:9 by gas chromatography), IR (film) : 1687 cm ⁇ 1; 1H NMR (CDCl3): delta 10.58 (1H,s) ppm.
• Methyl (thianthren-1-yl)acetate (30.0g) was converted by the 2 steps described in Example 3, that is, by successive treatment with sodium hydride and methyl formate then potassium carbonate and dimethyl sulphate, into the title compound (19.72g, 57% yield) as a solid with mp. and spectroscopic data as described in Example 2 for the same compound.
• compositions suitable for agricultural and horticultural purposes which can be formulated from the compounds of the invention. Such compositions form another aspect of the invention.
• An emulsifiable concentrate is made up by mixing the ingredients, and stirring the mixture until all the constituents are dissolved.
• Compound No. 1 of Table I 10% Isophorone 25% Calcium dodecylbenzenesulphonate 5% Nonylphenolethoxylate (13 moles ethylene oxide) 10% Alkyl benzenes 50%
• composition suitable for use as a seed dressing is prepared by grinding and mixing the three ingredients.
• Compound No. 3 of Table I 50% Mineral oil 2% China clay 48%
• a dustable powder is prepared by grinding and mixing the active ingredient with talc.
• Compound No. 4 of Table I 5% Talc 95%
• a suspension concentrate is prepared for chemicals which are largely insoluble solids by ball milling, for example, the constituents set out below, to form an aqueous suspension of the ground mixture with water.
• Compound No. 1 of Table I 40% Sodium lignosulphonate 10% Bentonite clay 1% Water 49%
• This formulation can be used as a spray by diluting into water or applied directly to seed.
• a wettable powder formulation is made by mixing together the ingredients set out below and then grinding the mixture until all are thoroughly mixed.
• Compound No. 3 of Table I 25% Sodium lauryl sulphate 2% Sodium lignosulphonate 5% Silica 25% China clay 43%
• the compounds were tested against a variety of foliar fungal diseases of plants.
• the technique employed was as follows.
• the plants were grown in John Innes Potting Compost (No 1 or 2) in 4cm diameter minipots.
• the test compounds were formulated by bead milling with aqueous Dispersol T and diluted to the required concentration immediately before use.
• the formulations 100 ppm active ingredient
• the sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
• Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.
• the disease control was recorded by the following grading :
• This Example illustrates the plant growth regulating properties of compounds 1, 2 and 3 of Table I when tested on a whole plant screen against two species of plant.
• the plant species are identified in Table III with the leaf stage at which they were sprayed.
• a formulation of each chemical was applied at 4000 ppm (4 kg/ha in a 1000 1/ha field volume) using a tracksprayer and a SS8004E (Teejet) nozzle.
• Blank means less than 10% effect. Phytotoxicity is scored on a 1-5 basis where

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
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• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1987
  • 1987-11-04 EP EP87309769A patent/EP0270252A3/fr not_active Withdrawn
  • 1987-11-12 US US07/119,485 patent/US4857545A/en not_active Expired - Fee Related
• 1989
  • 1989-06-12 US US07/365,015 patent/US4976771A/en not_active Expired - Fee Related

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